WO1991013859A1 - Composes contenant des unites d'oxide d'alkylene et des groupes quaternaires d'ammonium - Google Patents

Composes contenant des unites d'oxide d'alkylene et des groupes quaternaires d'ammonium Download PDF

Info

Publication number
WO1991013859A1
WO1991013859A1 PCT/EP1991/000386 EP9100386W WO9113859A1 WO 1991013859 A1 WO1991013859 A1 WO 1991013859A1 EP 9100386 W EP9100386 W EP 9100386W WO 9113859 A1 WO9113859 A1 WO 9113859A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
alkyl
water
quaternary ammonium
units
Prior art date
Application number
PCT/EP1991/000386
Other languages
German (de)
English (en)
Inventor
Ralf Bohlander
Günter Uphues
Uwe Ploog
Maria Liphard
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1991013859A1 publication Critical patent/WO1991013859A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/02—Working-up waste paper
    • D21C5/025—De-inking
    • D21C5/027—Chemicals therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Definitions

  • the invention relates to water-soluble or water-dispersible compounds containing alkylene oxide units and quaternary ammonium groups, a process for their preparation and the use of these compounds for removing printing inks from printed waste paper and / or paper cycle water.
  • waste paper For the production of, for example, newspaper printing and hygiene papers, waste paper is used in large quantities today.
  • the quality of these types of paper is determined by their brightness and color.
  • the printing inks In order to be able to produce high quality paper types, the printing inks have to be removed from the printed waste paper. This is usually done using deinking processes, which essentially take place in two steps:
  • the second process step can be carried out by washing or flotation (Ullmann's Enzyclopadie der Technischen Chemie, 4th edition, volume 17, pages 570-571 (1979)).
  • flotation in which the different wettability of printing inks and paper fibers is used, air is pressed or sucked through the paper stock suspensions. Small air bubbles combine with the ink particles and form a foam on the surface of the water, which is removed with fabric hangers.
  • the deinking of waste paper is usually carried out at alkaline pH values in the presence of alkali hydroxides, alkali silicates, oxidizing bleaches and surface-active substances at temperatures between 30 and 50 ° C.
  • Soaps and / or fatty alcohol polyglycol ethers are predominantly used as surface-active substances which bring about the detachment and separation of the printing ink particles (Ullmann's Enzyclopadie der Technischen Chemie, 4th edition, volume 17, pages 571-572 (1979)).
  • alkylamine polyethers to remove printing ink is described in German Offenlegungsschrift DE-OS 33 22 330 and in German Patent DE-PS 33 47 906. Furthermore, from JP 84/137587, referenced in Che.
  • water-thinnable printing inks have decisive advantages over conventional solvent-based printing inks, there are still warnings about the introduction of processes using water-thinning printing inks (flexographic printing inks), since water-thinnable printing inks made from waste paper contain the usual surfactants from the deinking fleet - if at all - can only be removed completely inadequately (Das Textil 42 (10 A), V84-V88 (1988)). The result of this is that to date the accumulating waste paper that has been printed in water-thinnable printing inks is not being recycled and is therefore not available as waste paper raw material for newsprint and hygienic paper.
  • the object underlying the invention was therefore to provide compounds for deinking waste paper, with which it is possible to remove, in particular, water-dilutable printing inks from waste paper in satisfactory amounts.
  • the invention accordingly relates to water-soluble or water-dispersible compounds containing alkylene oxide units and quaternary ammonium groups, which can be prepared by quaternizing tertiary amines of the general formula
  • R 1 denotes (AO) -H
  • R 2 and R 3 are identical or different and each represents R * or a C * _22-alkyl group with or without OH, NR 4 R 5 and / or NHC0R 6 groups
  • R 4 and R 5 are identical or different and in each case mean H or a C 4 alkyl group
  • R 5 is a C 2 alkyl group
  • AO represents 1 to 95 alkylene oxide units which are composed of 0 to 60 C2H4 ⁇ units and 0 to Assemble 35 C3HöO units, with C22-ATyl halides, benzyl halides, di-22-alkyl sulfates, tri-22-alkyl phosphates, 22 -22 alkyl tosylates and / or epoxy compounds, then reaction with epihalohydrins and then reaction of the compounds obtained alone or in combination with Halogenohydrin compounds which do not contain any quaternary ammonium groups, with ammonia, C22 alkyl
  • Another object of the invention is a method for producing water-soluble or water-dispersible, alkylene oxide units and compounds containing quaternary ammonium groups, which is characterized in that tertiary amines of the general formula
  • R 1 denotes (AO) -H
  • R 2 and R 3 are identical or different and in each case R 1 or a Ci ⁇ alkyl group m ⁇ oc * er onne OH-, NR 4 R 5 - and / or NHC0R 5 - Mean groups
  • R 4 and R 5 are identical or different and in each case mean H or a C 4 alkyl group
  • R 6 represents a C * .2i alkyl group
  • AO represents 1 to 95 alkylene oxide units, which are composed of 0 to 60 Assemble C2H4 ⁇ units and 0 to 35 C3H6 ⁇ units with Benzyl halides, di-C ⁇ _22- a l ylsul- faten, tri-C ⁇ _22-alkyl phosphates, quaternized C ⁇ _22 "alkyl tosylates and / or epoxy compounds,
  • the polyethers described in DE-PS 38 03 213 have significantly lower molar masses and only have terminal quaternary ammonium groups and at least one oxirane group.
  • the starting materials for the preparation of the compounds according to the invention are tertiary amines of the general formula Rl
  • radicals R 1, R 2 and R 3 have the abovementioned meanings, for example cocosamines alkoxylated with 2 to 30 mol of ethylene oxide, dimethylamino-propylamines alkoxylated with 2 to 30 mol of ethylene oxide and methylamines alkoxylated with 2 to 30 mol of ethylene oxide and / or monoacylated aminoethylethanolamines alkoxylated with 1 to 30 moles of ethylene oxide.
  • the quaternization of the tertiary amines is carried out in a manner known per se at temperatures preferably between 40 and 130 ° C., particularly preferably between 70 and 100 ° C.
  • quaternizing agents are C * ⁇ _4-alkyl halides such as methyl chloride, ethyl chloride and / or butyl chloride, benzyl chloride, di-C ⁇ _4-alkyl sulfates, such as dimethyl sulfate, ethylene oxide, propylene oxide and / or glycidol. If epoxy compounds are used for quaternization, the amines are first converted into the corresponding protonated form with acids in accordance with DE 35 26 600 or DE 36 18 944.
  • the compounds obtained, containing alkylene oxide units and quaternary ammonium groups are optionally freed from solvents, for example water and / or C 1-4 alkyl alcohols, and at temperatures preferably between 60 and 120 ° C., particularly preferably between 70 and 95 ° C. with epihalohydrins, preferably epichlorohydrin, in the presence of catalysts, for example, boron trifluoride or tin tetrachloride.
  • the epihalohydrins are used, based on an OH function, in amounts of preferably 0.6 to 4 mol, particularly preferably 0.8 to 1.2 mol.
  • the compounds obtained are then preferably in combination with halohydrin compounds which contain no quaternary ammonium groups, without solvents or in the form of, in particular, aqueous solutions with ammonia, C22 -22 alkylamines, aliphatic di- and / or polyamines and / or amino sugars at temperatures between preferably 40 and 120 ° C, particularly preferably between 60 and 95 ° C, brought to reaction.
  • the reactions are preferably carried out with, based on halohydrin groups, 0.1 to 20 amine equivalents, particularly preferably 0.2 to 1.3 amine equivalents, C * 22 -alkyla ⁇ nen and / or aliphatic di- and / or polyamines.
  • Suitable linear, branched-chain or cyclic C22 alkylamines are, for example, dodecylamine, 2-ethylhexylamine, coconut amine and / or talga in.
  • optionally alkoxylated di- and / or polyamines which optionally Amide groups in the aliphatic radicals are suitable, for example, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, dihexaethylenetriamine, 1,2-dihydroxyethyldiaminoethane, piperazine, polyethyleneimines with average molecular weights between 200 and 10,000, bis- [3, 3-aminopropyl] methylamine, N, N-dimethylaminopropylamine, N-stearylpropylenediamine and / or N-acylamidoamine, can be prepared by aminolysis of
  • Alkoxylated, preferably ethoxylated, di- and / or polyamines must have at least one NH group.
  • the reactions with ammonia and / or amine compounds are preferably carried out in the presence of bases, for example alkali metal hydroxides.
  • the quaternary ammonium compounds reacted with epihalohydrins, preferably with halohydrin compounds which do not contain quaternary ammonium groups, in particular with bischlorohydrin ethers based on polyethylene glycols, polypropylene glycols and / or polytetrahydrofurans, in a weight ratio with epihalogenohydrates reacted quaternary ammonium compounds to compounds without quaternary ammonium groups 0.1: 10 to 10: 1, if appropriate in the presence of alkali metal hydroxides.
  • the reactions are terminated by adding inorganic and / or organic acids, for example hydrochloric acid, acetic acid and / or lactic acid.
  • inorganic and / or organic acids for example hydrochloric acid, acetic acid and / or lactic acid.
  • the compounds according to the invention are aqueous solutions or gels which form aqueous solutions with water and contain the compounds according to the invention in amounts of 10 to 80% by weight, preferably 20 to 60% by weight.
  • the compounds according to the invention are added to paper stock suspensions, preferably in amounts of 0.02 to 2% by weight, particularly preferably from 0.1 to 0.5% by weight, in each case based on air-dry paper stock.
  • Air-dry paper stock means that an equilibrium state of internal moisture has occurred in the paper stock. This state of equilibrium depends on the temperature and the relative humidity of the air.
  • the deinking result ie the removal of printing inks from printed waste paper
  • the compounds according to the invention in combination with, for example, Ci0-22 "' ettsa ⁇ jren ' are 01inor R 4010, 01inor R 4020 and / or 01inor R DG40 (manufacturer of all Henkel KGaA products), ethoxylated alkyl alcohols with 6 to 22 carbon atoms, ethoxylated alkylphenols, polymers such as polyacrylamides and / or polydimethylaminoethyl methacrylates and / or copolymers, described for example in DE 38 39 479, in amounts of 0. 01 to 1% by weight, based on air-dry paper stock, and / or with layer compounds of the general composition which have been precipitated in situ
  • M (II) stands for divalent metal cations
  • M (III) for trivalent metal cations
  • the molar ratio of divalent metal cations to trivalent metal cations in layer compounds precipitated in situ is preferably between 20: 1 and 1: 1, based on air-dry paper stock trivalent metal cations can be used in amounts between 0.3 and 2% by weight.
  • water-thinnable and / or solvent-containing printing inks preferably water-thinning printing inks
  • solvent-containing printing inks for example newspaper rotary inks, letterpress inks, off-set printing inks, gravure inks, flexographic inks, laser inks and / or rotogravure printing inks from printed waste paper, for example newspapers, magazines, computer papers, magazines, brochures, forms, telephone books and / or catalogs.
  • the waste papers deinked using the compounds according to the invention are distinguished by very high degrees of whiteness.
  • Printed waste papers are, for example, between 1 and 5% by weight in a cloth dissolver in aqueous solution, which typically contains 0 to 1.5% by weight hydrogen peroxide (100%), 0 to 2.5% by weight. 99% by weight NaOH and 0 to 4.0% by weight soda water glass with a solids content of 35% by weight (37 to 40 ° Be) - all% by weight information relates to air-dry paper stock , crushed at temperatures between 20 and 60 ° C. The pulp suspensions are then stirred into water or water is added, so that 0.6 to 1.6% by weight pulp suspensions are obtained.
  • Flotation is preferably carried out in a manner known per se, for example in a Denver flotation cell.
  • fatty acids for example fatty acids, ethoxylated alkyl alcohols and / or alkylphenols, polymers, copolymers and / or layer compounds precipitated in situ, can be used these are added to the paper stock suspensions before or during the comminution of the paper stock or together with the compounds according to the invention.
  • printing inks are removed both from the waste paper and from the circulating water.
  • the compounds according to the invention can also be used for the separate cleaning of paper circulation waters. In these cases, after the addition of 2 to 100 mg of compounds according to the invention per liter of circulating water, the printing ink particles are eliminated, for example by filtration or flotation.
  • the deinkability index (DEM) was calculated from the reflection factors R457 nm (whiteness) of the printed (BS), deinked (DS) and unprinted (US) paper stock using the following formula:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Paper (AREA)

Abstract

L'invention concerne des composés solubles ou dispersibles dans l'eau qui contiennent des unités d'oxyde d'alkylène et des groupes quaternaires d'ammonium, leur procédé de production et leur utilisation afin d'éliminer l'encre d'impression de vieux papiers imprimés et/ou des eaux remises en circulation dans l'industrie de fabrication de papier.
PCT/EP1991/000386 1990-03-09 1991-03-01 Composes contenant des unites d'oxide d'alkylene et des groupes quaternaires d'ammonium WO1991013859A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904007596 DE4007596A1 (de) 1990-03-09 1990-03-09 Alkylenoxideinheiten und quaternaere ammoniumgruppen enthaltende verbindungen
DEP4007596.6 1990-03-09

Publications (1)

Publication Number Publication Date
WO1991013859A1 true WO1991013859A1 (fr) 1991-09-19

Family

ID=6401859

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/000386 WO1991013859A1 (fr) 1990-03-09 1991-03-01 Composes contenant des unites d'oxide d'alkylene et des groupes quaternaires d'ammonium

Country Status (3)

Country Link
AU (1) AU7455191A (fr)
DE (1) DE4007596A1 (fr)
WO (1) WO1991013859A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592789A2 (fr) * 1992-09-14 1994-04-20 Rheox International, Inc. Procédé pour désencrer du vieux papier en utilisant des argiles organiques produites in situ
EP0622490A2 (fr) * 1993-04-26 1994-11-02 Rheox International, Inc. Procédé pour élimination des composants inorganiques produisant des cendres par combustion et des résidus huileux lors du recyclage du papier
EP0684223A1 (fr) * 1994-05-23 1995-11-29 Hoechst Aktiengesellschaft Quaternisation d'amines tertiaires avec le diméthylsulphate en l'absence de solvant

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4313085A1 (de) * 1993-04-21 1994-10-27 Stockhausen Chem Fab Gmbh Stabile wäßrige Dispersionen von quartären Ammoniumverbindungen und Imidazolin-Derivaten
DE19631150B4 (de) * 1996-08-01 2007-04-19 Süd-Chemie AG Verfahren zur Ablösung von Druckfarben (Deinking) von cellulosehaltigen Druckträgern
AU6898598A (en) * 1997-04-10 1998-10-30 Rhodia Inc. Process for removing waterborne flexographic inks from substrates
US7169257B2 (en) 2003-11-12 2007-01-30 Kemira Chemicals, Inc. Method of deinking waste paper using a reduced alkali system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3591520A (en) * 1968-01-17 1971-07-06 Nalco Chemical Co Quaternary adducts of polyepihalohydrin and use thereof
EP0013027A1 (fr) * 1978-12-30 1980-07-09 Henkel Kommanditgesellschaft auf Aktien Procédé de désencrage de vieux papiers imprimés
GB2116966A (en) * 1982-02-26 1983-10-05 British Petroleum Co Plc Aqueous compositions of N-oxyalkylated quaternary ammonium salt surfactants
US4451671A (en) * 1981-09-12 1984-05-29 Hoechst Aktiengesellschaft Cationic ethylene oxide/propylene oxide and ethylene oxide/butylene oxide polymers, a process for their preparation and their use
EP0171370A1 (fr) * 1984-03-19 1986-02-12 Berol Kemi Ab Procédé d'élimination de l'encre et/ou d'adhésion dans le traitement des vieux papiers
DE3816200A1 (de) * 1987-05-12 1988-11-24 Seppic Sa Neue kationische oberflaechenaktive mittel vom quaternaeren ammonium-typ, verfahren zu deren herstellung und deren verwendung, insbesondere zur behandlung von textilien und zellulosematerialien

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3591520A (en) * 1968-01-17 1971-07-06 Nalco Chemical Co Quaternary adducts of polyepihalohydrin and use thereof
EP0013027A1 (fr) * 1978-12-30 1980-07-09 Henkel Kommanditgesellschaft auf Aktien Procédé de désencrage de vieux papiers imprimés
US4451671A (en) * 1981-09-12 1984-05-29 Hoechst Aktiengesellschaft Cationic ethylene oxide/propylene oxide and ethylene oxide/butylene oxide polymers, a process for their preparation and their use
GB2116966A (en) * 1982-02-26 1983-10-05 British Petroleum Co Plc Aqueous compositions of N-oxyalkylated quaternary ammonium salt surfactants
EP0171370A1 (fr) * 1984-03-19 1986-02-12 Berol Kemi Ab Procédé d'élimination de l'encre et/ou d'adhésion dans le traitement des vieux papiers
DE3816200A1 (de) * 1987-05-12 1988-11-24 Seppic Sa Neue kationische oberflaechenaktive mittel vom quaternaeren ammonium-typ, verfahren zu deren herstellung und deren verwendung, insbesondere zur behandlung von textilien und zellulosematerialien

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592789A2 (fr) * 1992-09-14 1994-04-20 Rheox International, Inc. Procédé pour désencrer du vieux papier en utilisant des argiles organiques produites in situ
EP0592789A3 (fr) * 1992-09-14 1995-07-12 Rheox Int Procédé pour désencrer du vieux papier en utilisant des argiles organiques produites in situ.
EP0622490A2 (fr) * 1993-04-26 1994-11-02 Rheox International, Inc. Procédé pour élimination des composants inorganiques produisant des cendres par combustion et des résidus huileux lors du recyclage du papier
EP0622490A3 (fr) * 1993-04-26 1995-07-12 Rheox Int Procédé pour élimination des composants inorganiques produisant des cendres par combustion et des résidus huileux lors du recyclage du papier.
EP0684223A1 (fr) * 1994-05-23 1995-11-29 Hoechst Aktiengesellschaft Quaternisation d'amines tertiaires avec le diméthylsulphate en l'absence de solvant

Also Published As

Publication number Publication date
AU7455191A (en) 1991-10-10
DE4007596A1 (de) 1991-09-12

Similar Documents

Publication Publication Date Title
AT401780B (de) Verfahren zum de-inken von altpapier
EP0074558B1 (fr) Procédé pour la fabrication de produits de condensation soluble dans l'eau et contenant de l'azote et leur usage dans la fabrication du papier
EP0282862B1 (fr) Composés contenant de l'azote, solubles dans l'eau
DE2434816B2 (de) Verfahren zur Herstellung von stickstoffhaltigen Kondensationsprodukten und deren Verwendung als Retentionsmittel, Flockungsmittel und Entwässerungsbeschleuniger bei der Papierherstellung
DE2436386C2 (de) Verwendung stickstoffhaltiger Kondensationsprodukte
EP0553138B1 (fr) Utilisation de composes contenant des chaines polyethers et extraits de derives d'acide carboxylique epoxyde afin d'eliminer les encres d'impression de vieux papiers et/ou d'eaux de recyclage de papier
WO1991001405A1 (fr) Procede de traitement des vieux papiers
EP0061173B1 (fr) Procédé de coloration du papier
WO1991013859A1 (fr) Composes contenant des unites d'oxide d'alkylene et des groupes quaternaires d'ammonium
DE69725568T2 (de) Verfahren zur druckfarbenentfernung
EP0031899B1 (fr) Produits de réaction auto-réticulables et solubles dans l'eau, procédé de préparation de liants à partir de ceux-ci, et leur utilisation pour l'amélioration de la résistance à l'état humide du papier
EP0464057B1 (fr) Procede de recuperation de vieux papiers
WO1991013924A1 (fr) Composes solubles ou dispersibles dans l'eau contenant des chaines de polyether et des groupes quaternaires d'ammonium
EP0372267B1 (fr) Désencrage de vieux papiers
WO1991013926A1 (fr) Composes contenant des chaines de polyether et des groupes quaternaires d'ammonium
EP0513782B1 (fr) Agents surfactants, qui contiennent la nitrogen et qui sont dérivés des acides résiniques
EP0013027B1 (fr) Procédé de désencrage de vieux papiers imprimés
EP0494152B1 (fr) Emploi de polymeres au moins partiellement hydrosolubles pour eliminer des encres d'imprimerie contenues dans les vieux papiers imprimes et/ou l'eau de recyclage dans l'insdustrie papetiere
WO1991003596A1 (fr) Utilisation de composes contenant des chaines d'oxydes de polyalkylene et de l'azote pour eliminer les encres d'imprimerie sur les vieux papiers imprimes et/ou dans les eaux de recyclage du papier
WO1993015260A1 (fr) Procede pour l'elimination d'encres d'imprimerie dans des vieux papiers imprimes
DE3816200C2 (de) Neue kationische oberflächenaktive Mittel vom quaternären Ammonium-Typ, Verfahren zu deren Herstellung und deren Verwendung, insbesondere zur Behandlung von Textilien und Zellulosematerialien
DE2026449B2 (de) Verfahren zur herstellung von wasserloeslichen stickstoffhaltigen polykondensaten
EP0793748A1 (fr) Procede permettant d'eliminer les encres d'imprimerie presentes sur des papiers de recuperation
EP2048282A1 (fr) Utilisation de produits de condensation d'acides gras pour l'augmentation du volume de papier et de carton
DE3913667A1 (de) Pigmentzubereitungen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA